CN112505114A - Preparation of all-polymer self-supporting electrode and application of all-polymer self-supporting electrode in flexible electrochemical sensor - Google Patents
Preparation of all-polymer self-supporting electrode and application of all-polymer self-supporting electrode in flexible electrochemical sensor Download PDFInfo
- Publication number
- CN112505114A CN112505114A CN202011361833.2A CN202011361833A CN112505114A CN 112505114 A CN112505114 A CN 112505114A CN 202011361833 A CN202011361833 A CN 202011361833A CN 112505114 A CN112505114 A CN 112505114A
- Authority
- CN
- China
- Prior art keywords
- electrode
- pee
- polypyrrole
- film
- ppy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 84
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 229960003638 dopamine Drugs 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 6
- 239000002482 conductive additive Substances 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012074 organic phase Substances 0.000 claims abstract description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 13
- VFFFESPCCPXZOQ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.OCC(CO)(CO)CO VFFFESPCCPXZOQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000008346 aqueous phase Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229920006254 polymer film Polymers 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 229940080296 2-naphthalenesulfonate Drugs 0.000 claims description 3
- 239000013504 Triton X-100 Substances 0.000 claims description 3
- 229920004890 Triton X-100 Polymers 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000970 chrono-amperometry Methods 0.000 claims description 3
- KVBGVZZKJNLNJU-UHFFFAOYSA-M naphthalene-2-sulfonate Chemical compound C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-M 0.000 claims description 3
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 40
- 238000001514 detection method Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 230000004044 response Effects 0.000 description 9
- 239000004020 conductor Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 229920005839 ecoflex® Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
Abstract
The invention discloses a preparation method of an all-polymer self-supporting electrode and application thereof in a flexible electrochemical sensor, relating to the technical field of electrochemical sensors and comprising the following steps: a) the polypyrrole film with the sandwich structure is prepared by adopting an electrochemical polymerization method, the pentaerythritol ethoxylate-polypyrrole (PEE-PPy) film is synthesized in an organic phase system, namely in an organic electrolyte by adopting an electrochemical polymerization mode, a working electrode is a glass sheet plated with titanium and platinum in sequence, a counter electrode is a stainless steel electrode, and a reference electrode is a silver wire. The polypyrrole composite film with the sandwich structure is used as the self-supporting electrode for detecting dopamine in the flexible electrochemical sensor, and the sensor does not need to be combined with an additional current collector, a mechanical substrate, a conductive additive and the like to assemble the sensor, so that the polypyrrole composite film has high sensitivity and high stability for detecting dopamine, and has the capacity of bearing long-term mechanical deformation.
Description
Technical Field
The invention relates to the technical field of electrochemical sensors, in particular to preparation of an all-polymer self-supporting electrode and application of the all-polymer self-supporting electrode in a flexible electrochemical sensor.
Background
In recent years, with the rapid development of mobile internet and intelligent terminals, wearable electronic devices have shown a huge market prospect, and a flexible wearable electronic sensor as one of core components has become a focus of attention by the characteristics of wide range, high sensitivity, rapid response time, portability, use comfort, multifunctional integration and the like of the device, so that research and development of domestic and foreign researchers on the flexible wearable electronic sensor are stimulated. The flexible electrochemical sensor can realize real-time health monitoring of a human body by converting chemical signals into electric signals. The current research is mainly to achieve flexibility and wearability of electrochemical sensors by integrating the sensing unit with flexible polymer substrates or wearable items (clothes, gloves, glasses, etc.). For flexible electrochemical sensors, the study of flexible deformable conductive electrodes is a very critical step. Researchers mainly prepare flexible electrodes by two design methods, one is to design electrodes with stretchable structures, and design electrode circuit patterns of snakes, waves, spirals and the like by technologies such as photoetching or pre-stretching, and the other is to prepare electrode materials with synthetic inherent stretchability, and by incorporating active conductive additive materials (graphene, carbon nanotubes, carbon black, conductive polymers and the like) into an elastic substrate (PDMS, polyimide, polyurethane, Ecoflex and other elastomers), combining the conductivity of the conductive materials and the elasticity of the substrate, a flexible and deformable conductive electrode is finally obtained. In actual research work, researchers usually combine the two methods to design and prepare flexible conductive electrodes. Researchers have undertaken a series of work in designing conductive electrodes that are resistant to mechanical deformation, for example, printing conductive PEDOT: PSS and Ag/AgCl inks onto elastomeric substrates to prepare flexible electrochemical sensors; and growing the synthesized gold nano-wire in situ on the elastic substrate to serve as a stretchable electrochemical electrode. Although these electrochemical sensors designed by researchers can endure mechanical deformation to a certain extent, they still need to rely on an additional elastic substrate to obtain flexibility, and when applied to a flexible electrochemical sensor, due to the significant difference of modulus between the conductive material and the substrate, repeated mechanical deformation can cause peeling and delamination between the conductive material and the substrate, which seriously affects the durability and stability of the electrochemical sensor, therefore, it is important to design and prepare a self-supporting electrode which has inherent conductivity and excellent mechanical properties and can be separated from the elastic substrate for the flexible electrochemical sensor. To this end, we propose to prepare an all-polymer self-supporting electrode and apply it to a flexible electrochemical sensor to solve this problem.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides preparation of a full-polymer self-supporting electrode and application of the full-polymer self-supporting electrode in a flexible electrochemical sensor, and on one hand, the problems of poor mechanical property, low mechanical strength and poor flexibility of the flexible self-supporting electrode reported at present are solved. On the other hand, when the flexible conductive electrode is applied to a flexible electrochemical sensor, the modulus between the conductive material and the substrate is obviously different, and the conductive material and the substrate are peeled and layered due to repeated mechanical deformation, so that the durability and the stability of the flexible electrochemical sensor are seriously affected.
(II) technical scheme
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows: the preparation method of the all-polymer self-supporting electrode is characterized by comprising the following steps of:
a) synthesizing PEE-PPy in organic phase system, i.e. organic electrolyte, by electrochemical polymerization, and the working electrode is successively platedThe titanium and platinum glass sheet uses a stainless steel counter electrode and a silver wire as a reference electrode, and adopts constant current polymerization with the current density of 0.8-1.0mA/cm2And polymerizing for 90min under the ice-water bath condition, and finally peeling off the PEE-PPy film from the upper surface of the electrode, wherein the final thickness of the PEE-PPy film is 15 mu m.
b) After the PEE-PPy film is prepared, the prepared PEE-PPy film is used as a working electrode in an aqueous phase system, namely aqueous electrolyte, meanwhile Ag/AgCl is used as a reference electrode, a stainless steel electrode is used as a counter electrode, 2-naphthalene sulfonate doped polypyrrole is continuously synthesized on the surface of the PEE-PPy film, and then the aqueous phase polypyrrole is polymerized on the two surfaces of the PEE-PPy film. The polymerization mode is constant voltage, the specific polymerization voltage is set to be 0.87V, and the polymerization is carried out for 20min in ice-water bath, so that the polypyrrole composite film with the sandwich structure is finally obtained.
Preferably, the organic electrolytic solution is prepared by: isopropanol and boron trifluoride diethyl etherate solution are mixed in a volume ratio of 7:3, then 5% PEE in volume ratio is added, and finally pyrrole monomer is added, wherein the specific concentration of pyrrole is 0.05M.
Preferably, the preparation of the aqueous electrolyte is as follows: pyrrole monomer (0.05M) and 2-sodium naphthalenesulfonate (0.1M) are added into the aqueous solution in sequence, Triton X-100 with the concentration of 0.025M is selected as a surfactant, and the pH of the electrolyte is adjusted to 3 by using 2-naphthalenesulfonic acid.
Preferably, the pentaerythritol ethoxylate-polypyrrole is polypyrrole doped with pentaerythritol ethoxylate (PEE) synthesized by electrochemical polymerization (PPy), which is abbreviated as PEE-PPy.
Preferably, the equipment for synthesizing the PEE-PPy and the polypyrrole composite film with the sandwich structure is Chenghua electrochemical workstation 660E.
Preferably, the stainless steel electrode is 304.
Preferably, the method for preparing the sandwich structure takes a synthesized PEE-PPy film as a working electrode and grows polypyrrole on the surface of the working electrode in an aqueous phase system, and finally the polypyrrole composite film with the sandwich structure is obtained.
An application of an all-polymer self-supporting electrode in a flexible electrochemical sensor is disclosed, which comprises the following specific modes: the polypyrrole with the sandwich structure is used as a material for forming an all-polymer film electrode, the all-polymer film electrode is directly used as a working electrode and is simultaneously connected with an electrochemical workstation, then a saturated calomel electrode and a platinum wire are respectively used as a reference electrode and a counter electrode, so that a flexible electrochemical sensor is formed, and dopamine is detected by a chronoamperometry (i-t). The all-polymer self-supporting electrode formed by the polypyrrole composite film with the sandwich structure can be directly used for a flexible electrochemical sensor, and the flexible electrochemical sensor does not need an additional current collector, a mechanical substrate and a conductive additive, and is simple to assemble, high in stability and good in flexibility.
(III) advantageous effects
The invention has the beneficial effects that:
1. the preparation method of the all-polymer self-supporting electrode and the application of the all-polymer self-supporting electrode in the flexible electrochemical sensor are characterized in that a PEE-PPy film with excellent conductivity is prepared by adopting an electrochemical polymerization method, the PEE-PPy film is directly used as a working electrode, polypyrrole under an aqueous phase system is polymerized in situ on two surfaces of the PEE-PPy film, and finally the polypyrrole composite film with a sandwich structure is obtained.
2. The preparation of the all-polymer self-supporting electrode and the application of the all-polymer self-supporting electrode in a flexible electrochemical sensor overcome the problems of poor mechanical property, low mechanical strength and poor flexibility of the flexible self-supporting electrode reported at present through the excellent mechanical property of a film material.
3. The preparation of the all-polymer self-supporting electrode and the application of the all-polymer self-supporting electrode in a flexible electrochemical sensor are realized, the mechanical supporting effect and flexibility are provided by separating an additional elastic substrate through the excellent mechanical property and self-supporting property of the film, and the conductivity of the film is high and stable. When the flexible conductive electrode is applied to a flexible electrochemical sensor, the modulus between a conductive material and a substrate is obviously different, and the conductive material and the substrate are peeled and layered due to repeated mechanical deformation, so that the durability and the stability of the flexible electrochemical sensor are seriously affected.
4. The preparation of the all-polymer self-supporting electrode and the application of the all-polymer self-supporting electrode in the flexible electrochemical sensor can be directly used as a working electrode of the flexible sensor to detect dopamine by virtue of excellent mechanical property and conductivity when being applied to the flexible electrochemical sensor, the process is simple, the processing flow of the traditional flexible electrochemical sensor is simplified, and the practicability of the all-polymer self-supporting electrode is further improved.
Drawings
FIG. 1 is a schematic structural diagram of a process for preparing a flexible full-polymer self-supporting electrode for dopamine detection according to the present invention;
FIG. 2 is a structural diagram of a stress-strain curve of a polypyrrole composite film according to the invention;
FIG. 3 is a structural diagram illustrating the long-term stability test of the conductivity of the polypyrrole composite thin film of the present invention in a PBS (0.1mM) solution;
FIG. 4 is a structural diagram of the polypyrrole composite film of the invention responding to the current of dopamine, the detection voltage is 0.45V, and dopamine (10mM) is detected in PBS (0.1mM, pH 6);
FIG. 5 shows the detection voltage and pH optimization of the present invention. (a) PPy composite films responded to i-t with dopamine at different voltages in PBS (0.1mM, pH 6). (b) Structural schematic of i-t response of PPy composite films to dopamine in PBS (0.1mM) at different pH values;
fig. 6 is a graph showing the current response of the all-polymer-based electrochemical sensor of the present invention to dopamine. The inset is a linear calibration curve for current and dopamine concentration. Schematic structure of experiments performed in 0.45V, PBS (0.1mM, pH6) solution;
FIG. 7 is a graph illustrating the long term stability of an all-polymer based electrochemical sensor of the present invention. A schematic diagram of an i-t experiment performed in a 0.45V, PBS (0.1mM, pH6) solution at a dopamine concentration of 10 mM;
FIG. 8 is a structural diagram showing the current response change of the full polymer thin film electrode of the present invention to dopamine before and after deformation (bending, twisting, folding and knotting), wherein the i-t experiment is performed in a 0.45V, PBS (0.1mM, pH6) solution, and the concentration of dopamine is 10 mM;
FIG. 9 is a structural diagram showing the stability of the electrochemical sensor after 1000 mechanical bending cycles of the all-polymer thin-film electrode of the present invention, i-t test is performed in 0.45V, PBS (0.1mM, pH6) solution, and the concentration of dopamine is 10 mM;
FIG. 10 is a structural diagram showing the current response of the all-polymer-based electrochemical sensor of the present invention to dopamine under different strains, wherein an i-t experiment is performed in a 0.45V, PBS (0.1mM, pH6) solution, and the concentration of the dopamine is 10 mM.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1 to 10, the present invention provides a technical solution: the preparation method of the all-polymer self-supporting electrode is characterized by comprising the following steps of:
a) synthesizing PEE-PPy in organic phase system, i.e. organic electrolyte, by electrochemical polymerization, wherein the working electrode is a glass sheet plated with titanium and platinum in sequence, the counter electrode is a stainless steel electrode, the reference electrode is a silver wire, and the current density is 0.8-1.0mA/cm2And polymerizing for 90min under the ice-water bath condition, and finally peeling off the PEE-PPy film from the upper surface of the electrode, wherein the final thickness of the PEE-PPy film is 15 mu m.
b) After the PEE-PPy film is prepared, the prepared PEE-PPy film is used as a working electrode in an aqueous phase system, namely aqueous electrolyte, meanwhile Ag/AgCl is used as a reference electrode, a stainless steel electrode is used as a counter electrode, 2-naphthalene sulfonate doped polypyrrole is continuously synthesized on the surface of the PEE-PPy film, and then the aqueous phase polypyrrole is polymerized on the two surfaces of the PEE-PPy film. The polymerization mode is constant voltage, the specific polymerization voltage is set to be 0.87V, and the polymerization is carried out for 20min in ice-water bath, so that the polypyrrole composite film with the sandwich structure is finally obtained.
Preparation of organic electrolyte: isopropanol and boron trifluoride diethyl etherate solution are mixed in a volume ratio of 7:3, then 5% PEE in volume ratio is added, and finally pyrrole monomer is added, wherein the specific concentration of pyrrole is 0.05M.
Preparing an aqueous electrolyte: pyrrole monomer (0.05M) and 2-sodium naphthalenesulfonate (0.1M) are added into the aqueous solution in sequence, Triton X-100 with the concentration of 0.025M is selected as a surfactant, and the pH of the electrolyte is adjusted to 3 by using 2-naphthalenesulfonic acid.
The pentaerythritol ethoxylate-polypyrrole is used for synthesizing pentaerythritol ethoxylate (PEE) doped polypyrrole (PPy) by electrochemical polymerization, and is called PEE-PPy for short.
The PEE-PPy and sandwich-structured polypyrrole composite film is synthesized by using Chenghua electrochemical workstation 660E.
The stainless steel electrode was used with model number 304.
The method for preparing the sandwich structure takes a synthesized PEE-PPy film as a working electrode, and polypyrrole in an aqueous phase system grows on the surface of the synthesized PEE-PPy film, so that the polypyrrole composite film with the sandwich structure is finally obtained.
An application of an all-polymer self-supporting electrode in a flexible electrochemical sensor is disclosed, which comprises the following specific modes: the polypyrrole composite film with the sandwich structure is a material for forming an all-polymer film electrode, the all-polymer film electrode is directly used as a working electrode and is simultaneously connected with an electrochemical workstation, then a saturated calomel electrode and a platinum wire are respectively used as a reference electrode and a counter electrode to further form a flexible electrochemical sensor, and dopamine is detected by a timing current method (i-t). The all-polymer self-supporting thin film electrode formed by the polypyrrole composite thin film has strong mechanical property, and as shown in figure 2, the all-polymer self-supporting thin film electrode has high mechanical strength (81.9MPa), high elongation at break (41.6%), good flexibility and low modulus (0.72 GPa). The material guideThe electrical properties were stable, as shown in fig. 3, and the conductivity remained at 99.1% after 30 days storage in PBS solution, and no additional elastomeric base material was required to provide flexibility and mechanical support, overcoming the problem of relying on elastomeric bases and conductive additives. In addition, the flexible electrochemical sensor formed by the all-polymer self-supporting electrode has high sensitivity, namely the high sensitivity is shown in the detection of dopamine, and as shown in fig. 6, the sensitivity of the sensor is 343.75 mu AmM-1cm-2Linear range of 1.0. mu.M-32.0. mu.M, R2The lowest detection limit was 0.9987, with a minimum detection limit of 0.49 μ M. Meanwhile, the polypyrrole composite film electrode has long-term stability, and as shown in fig. 7, after the polypyrrole composite film electrode is stored in PBS for 30 days, the current response to dopamine can still be maintained at 94.5%. And has mechanical deformation resistance, as shown in fig. 2 (the above mentioned mechanical performance diagram), the all-polymer film has good mechanical performance, high flexibility, and can generate various mechanical deformations, and when various mechanical deformations such as bending, twisting, folding, knotting and the like occur, the response current of the sensor hardly changes, as shown in fig. 8, the polypyrrole film with the sandwich structure as a whole has no additional elastic substrate, so that the problem that the conductive agent and the elastic substrate are peeled off in the mechanical deformation does not exist, which shows that the flexible electrochemical sensor has mechanical deformation resistance and stable sensing performance. Furthermore, long-term mechanical deformation also has no loss in sensor performance, as shown in fig. 9. The elongation at break of the film was high, and the current response retention of the sensor was 97.3% when 25% of mechanical deformation occurred, as shown in fig. 10. The experiments prove that the all-polymer-based flexible electrochemical sensor has good mechanical deformation stability, and can completely bear deformation motion of a human body when being applied to wearable detection, so that the all-polymer self-supporting electrode formed by the polypyrrole composite film with the sandwich structure can be used for the flexible electrochemical sensor, and is simple to assemble, high in stability and good in flexibility.
The method comprises the following operation steps:
the method comprises the steps of detecting by using a chronoamperometry (i-t), directly using an all-polymer film electrode formed by a polypyrrole composite film with a sandwich structure as a working electrode, simultaneously connecting the all-polymer film electrode with an electrochemical workstation, using a saturated calomel electrode and a platinum wire as a reference electrode and a counter electrode respectively, and then showing strong current response to dopamine by using the all-polymer flexible electrode, wherein detection voltage and pH value are optimized respectively as shown in figure 4, pH6 and 0.45V are optimal detection values as shown in figure 5, and further the application of the all-polymer self-supporting electrode in a flexible electrochemical sensor is realized.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only illustrative of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the all-polymer self-supporting electrode is characterized by comprising the following steps of:
a) synthesizing pentaerythritol ethoxylate (PEE) doped polypyrrole (PPy) in an organic phase system, namely in an organic electrolyte, in an electrochemical polymerization manner, wherein a working electrode is a glass sheet plated with titanium and platinum in sequence, a counter electrode is a stainless steel electrode, a reference electrode is a silver wire, polymerization is performed in a constant current manner, and the current density is 0.8-1.0mA/cm2And polymerizing for 90min under the ice-water bath condition, and finally peeling off the PEE-PPy film from the upper surface of the electrode, wherein the final thickness of the PEE-PPy film is 15 mu m.
b) After the PEE-PPy film is prepared, the prepared PEE-PPy film is used as a working electrode in an aqueous phase system, namely aqueous electrolyte, meanwhile Ag/AgCl is used as a reference electrode, a stainless steel electrode is used as a counter electrode, 2-naphthalene sulfonate doped polypyrrole is continuously synthesized on the surface of the PEE-PPy film, and then the aqueous polypyrrole is polymerized on two surfaces of the PEE-PPy film electrode. The polymerization mode is constant voltage, the specific polymerization voltage is set to be 0.87V, and the polymerization is carried out for 20min in ice-water bath, so that the polypyrrole composite film with the sandwich structure is finally obtained.
2. The preparation of the all-polymer self-supporting electrode according to claim 1, wherein the organic electrolyte is prepared by: isopropanol and boron trifluoride diethyl etherate solution are mixed in a volume ratio of 7:3, then 5% PEE in volume ratio is added, and finally pyrrole monomer is added, wherein the specific concentration of pyrrole is 0.05M.
3. The preparation method of the all-polymer self-supporting electrode according to claim 1, wherein the preparation of the aqueous electrolyte is as follows: pyrrole monomer (0.05M) and 2-sodium naphthalenesulfonate (0.1M) are added into the aqueous solution in sequence, Triton X-100 with the concentration of 0.025M is selected as a surfactant, and the pH of the electrolyte is adjusted to 3 by using 2-naphthalenesulfonic acid.
4. The preparation of the all-polymer self-supporting electrode according to claim 1, wherein: the pentaerythritol ethoxylate-polypyrrole is polypyrrole (PPy) doped with pentaerythritol ethoxylate (PEE) synthesized by electrochemical polymerization, and is called PEE-PPy for short.
5. The preparation of the all-polymer self-supporting electrode according to claim 1, wherein: the PEE-PPy and sandwich-structured polypyrrole composite film synthesis equipment selects Chenghua electrochemical workstation 660E.
6. The preparation of the all-polymer self-supporting electrode according to claim 1, wherein: the stainless steel electrode was used with model number 304.
7. The preparation of the all-polymer self-supporting electrode according to claim 1, wherein: the method for preparing the sandwich structure takes a synthesized PEE-PPy film as a working electrode and grows polypyrrole under an aqueous phase system on the surface of the working electrode, and finally the polypyrrole composite film with the sandwich structure is obtained.
8. The application of the all-polymer self-supporting electrode in the flexible electrochemical sensor according to claim 1 is as follows: the polypyrrole with the sandwich structure is used as a material for forming an all-polymer film electrode, the all-polymer film electrode is directly used as a working electrode and is simultaneously connected with an electrochemical workstation, then a saturated calomel electrode and a platinum wire are respectively used as a reference electrode and a counter electrode, so that a flexible electrochemical sensor is formed, and dopamine is detected by a chronoamperometry (i-t).
9. The use of the all-polymer self-supporting electrode according to claim 1 in a flexible electrochemical sensor is characterized by the following: the all-polymer self-supporting electrode formed by the polypyrrole composite film with the sandwich structure can be used for a flexible electrochemical sensor, and the flexible electrochemical sensor does not need an additional current collector, a mechanical substrate and a conductive additive, and is simple to assemble, high in stability and good in flexibility.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011361833.2A CN112505114A (en) | 2020-11-28 | 2020-11-28 | Preparation of all-polymer self-supporting electrode and application of all-polymer self-supporting electrode in flexible electrochemical sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011361833.2A CN112505114A (en) | 2020-11-28 | 2020-11-28 | Preparation of all-polymer self-supporting electrode and application of all-polymer self-supporting electrode in flexible electrochemical sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112505114A true CN112505114A (en) | 2021-03-16 |
Family
ID=74967055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011361833.2A Withdrawn CN112505114A (en) | 2020-11-28 | 2020-11-28 | Preparation of all-polymer self-supporting electrode and application of all-polymer self-supporting electrode in flexible electrochemical sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112505114A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112858408A (en) * | 2021-01-19 | 2021-05-28 | 青岛科技大学 | Flexible electrochemical biosensor and construction method thereof |
| CN113820368A (en) * | 2021-09-01 | 2021-12-21 | 青岛科技大学 | Self-supporting glucose sensor based on polypyrrole film and construction method thereof |
| CN114369241A (en) * | 2021-12-15 | 2022-04-19 | 华南理工大学 | Conductive polymer biosensor electrode material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080008824A1 (en) * | 2006-07-10 | 2008-01-10 | Samsung Electro-Mechanics Co., Ltd. | Method for manufacturing printed circuit board using imprinting |
| CN101816046A (en) * | 2007-10-05 | 2010-08-25 | 信越聚合物株式会社 | Conductive polymer solution, conductive coating film, and input device |
| CN106662789A (en) * | 2014-08-08 | 2017-05-10 | 株式会社理光 | Electrochromic element and electrochromic dimming element |
| CN110323078A (en) * | 2018-03-29 | 2019-10-11 | 中国科学技术大学 | A kind of electric polypyrrole self-supporting film electrode and preparation method thereof and a kind of flexible super capacitor and preparation method thereof |
-
2020
- 2020-11-28 CN CN202011361833.2A patent/CN112505114A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080008824A1 (en) * | 2006-07-10 | 2008-01-10 | Samsung Electro-Mechanics Co., Ltd. | Method for manufacturing printed circuit board using imprinting |
| CN101816046A (en) * | 2007-10-05 | 2010-08-25 | 信越聚合物株式会社 | Conductive polymer solution, conductive coating film, and input device |
| CN106662789A (en) * | 2014-08-08 | 2017-05-10 | 株式会社理光 | Electrochromic element and electrochromic dimming element |
| CN110323078A (en) * | 2018-03-29 | 2019-10-11 | 中国科学技术大学 | A kind of electric polypyrrole self-supporting film electrode and preparation method thereof and a kind of flexible super capacitor and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| DENGMING SUN ET AL.: "The construction of sea urchin spines-like polypyrrole arrays on cotton-based fabric electrode via a facile electropolymerization for high performance flexible solid-state supercapacitors", 《ELECTROCHIMICA ACTA》 * |
| FENGXIAN GAO ET AL.: "All-polymer free-standing electrodes for flexible electrochemical sensors", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| JYOTI NAYAK ET AL.: "Characteristics of flexible electrode made on cellulose by soluble polypyrrole coating", 《PROCEEDINGS OF THE INSTITUTION OF MECHANICAL ENGINEERS, PART C: JOURNAL OF MECHANICAL ENGINEERING SCIENCE》 * |
| L. F. WARREN ET AL.: "A Study of Conducting Polymer Morphology: The Effect of Dopant Anions Upon Order", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112858408A (en) * | 2021-01-19 | 2021-05-28 | 青岛科技大学 | Flexible electrochemical biosensor and construction method thereof |
| CN113820368A (en) * | 2021-09-01 | 2021-12-21 | 青岛科技大学 | Self-supporting glucose sensor based on polypyrrole film and construction method thereof |
| CN114369241A (en) * | 2021-12-15 | 2022-04-19 | 华南理工大学 | Conductive polymer biosensor electrode material and preparation method and application thereof |
| CN114369241B (en) * | 2021-12-15 | 2023-01-24 | 华南理工大学 | Conductive polymer biosensor electrode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112505114A (en) | Preparation of all-polymer self-supporting electrode and application of all-polymer self-supporting electrode in flexible electrochemical sensor | |
| Li et al. | Sodium alginate reinforced polyacrylamide/xanthan gum double network ionic hydrogels for stress sensing and self-powered wearable device applications | |
| Wang et al. | Sensors based on conductive polymers and their composites: a review | |
| Zhao et al. | A self-healing hydrogel electrolyte for flexible solid-state supercapacitors | |
| Li et al. | Wide temperature-tolerant polyaniline/cellulose/polyacrylamide hydrogels for high-performance supercapacitors and motion sensors | |
| Mondal et al. | High capacitance properties of polyaniline by electrochemical deposition on a porous carbon substrate | |
| Zhang et al. | Stretchable and conductive cellulose hydrogel electrolytes for flexible and foldable solid-state supercapacitors | |
| CN103401008A (en) | Method and device for storing bioelectrical energy by virtue of capacitive anode | |
| Li et al. | Bifunctional polyaniline electroconductive hydrogels with applications in supercapacitor and wearable strain sensors | |
| CN102779648B (en) | Preparation method for flexible electrode material for super capacitor | |
| CN113402651B (en) | Preparation method of high-strength self-healing hydrogel electrolyte, flexible supercapacitor assembled by high-strength self-healing hydrogel electrolyte and preparation method of flexible supercapacitor | |
| Chen et al. | Electrochemical capacitance of spherical nanoparticles formed by electrodeposition of intrinsic polypyrrole onto Au electrode | |
| CN108376618A (en) | Polyaniline/phytic acid conductive hydrogel and preparation method thereof and flexible super capacitor | |
| Gao et al. | All-polymer ultrathin flexible supercapacitors for electronic skin | |
| Zhou et al. | Dual-network polyvinyl alcohol/polyacrylamide/xanthan gum ionic conductive hydrogels for flexible electronic devices | |
| Zhao et al. | Self-powered sensor integration system based on thorn-like polyaniline composites for smart home applications | |
| Liu et al. | Preparation of flexible conductive composite electrode film of PEDOT: PSS/Aramid nanofibers via vacuum-assisted filtration and acid post-treatment for efficient solid-state supercapacitor | |
| CN112858408B (en) | Flexible electrochemical biosensor and construction method thereof | |
| CN101445618B (en) | A preparation method of self-supporting poly (3, 4- ethylenedioxythiophene) porous membrane | |
| Cai et al. | High performance flexible silk fabric electrodes with antibacterial, flame retardant and UV resistance for supercapacitors and sensors | |
| Ren et al. | In situ deposited multilayer integrated hydrogels for deformable and stretchable supercapacitors | |
| Wang et al. | Transparent, self-adhesive, highly environmental stable, and water-resistant ionogel enabled reliable strain/temperature sensors and underwater communicators | |
| Jiang et al. | Fabrication and seamless integration of insensitive-bending fully printed all-in-one fabric-based supercapacitors based on cost-effective MWCNT electrodes | |
| CN109786124B (en) | Flexible asymmetric supercapacitor and preparation method thereof | |
| Murthy et al. | Polypyrrole coated selective electrodes for iron-thionine photogalvanic cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210316 |